Cyanodithioimidocarbonates

ABSTRACT

UNSYMMETRICAL ESTERS OF CYANOIMIDODITHIOCARBONIC ACID AND THEIR PRODUCTION AND USES.

United States Patent (35w 3,658,901 CYANODITHIOIMIDOCARBONATES Richard J. Timmons, 222 Grand Ave., and Lawrence S. wiotaesibrook, 720 W. 5th St., both of Marysville, Ohio No Drawing. Continuation-impart of application Ser. No. 578,974, Sept. 13, 1966. This application June 18, 1969, Ser. No. 834,510

Int. Cl. C07c 12/00 US. Cl. 260-551 C 5 Claims ABSTRACT OF THE DISCLOSURE Unsymmetrical esters of cyanoimidodithiocarbonic acid and their production and uses.

RELATION TO OTHER APPLICATIONS an" (I) asc-u=c SCHZ where:

R is hydrogen or alkyl;

Z is hydrogen, alkyl, vinyl, substituted vinyl, phenyl, substituted phenyl, allyl, substituted allyl, alkoxy, alkoxyalkyl, carbamoyl, carboalkoxy, or cyano, or a heterocyclic radical;

R is an alkali metal, an alkaline earth metal, methyl, or

substituted methyl; and

CHZR is different from R.

Preferred are those compounds of Formula I where:

R is hydrogen or C -C alkyl;

Z is hydrogen; C -C alkyl; vinyl; halogen substituted vinyl; phenyl; phenyl substituted by one or more of the following: halogen, nitro, C -C alkoxy, and C -C alkyl; allyl; halogen substituted allyl; C -C alkoxy; C -C alkoxymethyl; C C alkoxy-ethyl; carba-moyl; C -C; car boalkoxy; pyridinyl; pyrimidyl; furyl; thienyl; or cyano; and R' is sodium; potassium; calcium; magnesium; methyl; or methyl substituted with one or more of the following: C -C alkyl, 'cyano, C -C carboalkoxy, phenyl, and phenyl with one or more substituents selected from halogen, nitro, C -C alkoxy, and C -C alkyl.

The following are representative of the compounds of the present invention:

Potassium methyl cyanoimidodithiocarbonate Potassium isopropyl cyanoimidodithiocarbonate Potassium n-butyl cyanoimidodithiocarbonate Potassium n-hexyl cyanoimidodithiocarbonate Potassium n-decyl cyanoimidodithiocarbonate Potassium s-butyl cyanoimidodithiocarbonate Potassium benzyl cyanoimidodithiocarbamate Potassium p-nitrobenzyl cyanoimidodithiocarbonate Potassium (3,4-methylenedioxy)benzyl cyanoimidodithiocarbonate Potassium pentafluorobenzyl cyanoimidodithiocarbonate Potassium allyl cyanoimidodithiocarbonate Potassium 2-chloroallyl cyanoimidodithiocarbonate Potassium 3,4,4-trifiuoro-3-butene cyanoimidodithiocarbonate 3,658,901 Patented Apr. 25, 1972 Potassium methoxymethyl cyanoimidodithiocarbonate Potassium 3-propanol cyanoimidodithiocarbonate Potassium ethoxyethyl cyanoimidodithiocarbonate Potassium ethoxycarbonylmethyl cyanoimidodithiocarbonate Potassium a-acetanilido cyanoimidodithiocarbonate' Potassium a-acetamido cyanoimidodithiocarbonate Potassium a-acetonitrile cyanoimidodithiocarbonate Potassium -picolyl cyanoimidodithiocarbonate Calcium butyl cyanoimidodithiocarbonate Sodium butyl cyanoimidodithiocarbonate Methyl n-butyl cyanoimidodithiocarbonate Methyl allyl cyanoirnidodithiocarbonate Methyl 2-chloroallyl cyanoimidodithiocarbonate Trimethylene bis (2-chloroallyl cyanoimidodithiocarbonate) n-Butyl n-decyl cyanoimidodithiocarbonate Ethyl isopropyl cyanoimidodithiocarbonate Methyl a-acetanilido cyanoimidodithiocarbonate Methyl N-ethylcarbamoylmethyl cyanoimidodithiocarbonate Methyl carbamoylmethyl cyanoimidodithiocarbonate Methyl carboxymethyl cyanoimidodithiocarbonate Methyl carbethoxy cyanoimidodithiocarbonate Methyl ethoxycarbonylmethyl cyanoimidodithiocarbonate Methyl N,N-dimethylcarbamoylmethyl cyanoimidodithiocarbonate I Butyl ethoxycarbonylmethyl cyanoimidodithiocarbonate Benzyl ethoxycarbonylmethyl cyanoimidodithiocarbonate Methyl (3,4-methylenedioxy)benzyl cyanoimidodithiocarbonate Methyl p-nitrobenzyl cyanoimidodithiocarbonate Methyl benzyl cyanoimidodithiocarbonate Methyl cyanomethyl cyanoimidodithiocarbonate Methyl methoxymethyl cyanoimidodithioearbonate The compounds of the present invention possess valuable pesticidal and other biological system growth regulating properties and are particularly distinguished by outstanding herbicidal, insecticidal, fungicidal, and fumigant type activities.

Compounds of the present invention having the formula astm,

therefore especially useful include, but are not necessarily limited to:

Potassium methyl cyanoimidodithiocarbonate Potassium isopropyl cyanoimidodithiocarbonate Potassium benzyl cyanoimidodithiocarbonate Potassium allyl cyanoimidodithiocarbonate Potassium ethoxyethyl cyanoimidodithiocarbonate Potassium a-acetanilido cyanoimidodithiocarbonate Many of these compounds are described in detail in copendmg application No. 803,411 filed Feb. 28, 1969, which is hereby incorporated by reference.

4 Sodium n-butyl cyanoimidodithiocarbonate halide with one mole of the dipotassium salt of cy- Calcium n-butyl cyanoimidodithiocarbonate anoimidodithiocarbonic acid; i.e., by dialkylation of the Those compounds of the present invention which are disalt.

unsymmetrical monoesters of cyanoimidodithiocarbonic The novel stepwise, monoalkylation reactions described acid (compounds of the Formula I where R is an alkali 5 herein are of course quite ditferent from that described or alkaline earth metal) can be prepared from salts of in the preceding paragraph in that, insofar as diesters are cyanoimidodithiocarbonic acid. Specifically, we have concerned, those produced by the previously described refound that, when a cyanoimidodithiocarbonate disalt of action are symmetrical while those of the present inventhe formula tion are unsymmetrical. Moreover, the novel monoesters s of the present invention are not produced by the previously reported reaction so that this reaction cannot be used to produce intermediates for the novel 1,2,4-thiadiazoles described in copending application No. 803,411.

In conjunction with the foregoing it is most unusual that Reaction 1 proceeds in the manner described above to produce the high yields we obtain in that the alkyl halide exhibits a preference for one of the two S-sites. From the DAmico patent cited above and the other literawherein M has the meaning assigned above and n is 1 15 when M is divalent and 2 when it is monovalent is brought into contact with an equimolar quantity of a substituted alkylhalide having the formula mm ture one would expect these sites to be unpreferentially l alkylated. That is, if equimolar amounts of the disalt and 2 alkyl halide were reacted, one would expect to obtain as where R and Z have the meanings assigned above and X the most likely result one-half mole of symmetrical d1- is chlorine, bromine, or iodine, a reaction occurs producester and one-half mole of unreacted dlsalt. Instead, as ing monoesters of cyanoimidodithiocarbonic acid having discussed above and as will become apparent from the Formula II. This reaction is illustrated by the following working examples hereinafter, this does not occur. The equation: alkyl halide instead shows a decided preference for one of Reaction 1; T a a, gm)

r 3 c 9 uen=e 4- as--u-:-.c-s=c i g (m) (m The other compounds of the present invention (unthe S-sites so that the product of the reaction is substansymmetrical diesters of cyanoimidodithiocarbonicw acid tially the unsymmetrical monoester, not the symmetrical having the Formula I where R is methyl or substituted diester. methyl) can be prepared from compounds of the Formula 40 The novel unsymmetrical esters of the present lnvention II by reacting the latter with equimolar amounts of subof course ditfer structurally from the symmetrical diesters stituted alkylhalides having the Formula RX where R produced by the prior art reaction. The symmetrical and X have the meanings assigned above and RX is difand unsymmetrical esters are also quite dissimilar in the ferent from RCHZX. This reaction proceeds as follows: yp 05 biological activity y p Moreover the two types of esters differ in that, as mentioned above, the Reaction 2: unsymmetrical esters of the present invention can be used s (M), S R to prepare the novel 1,2,4-thiadiazoles described in appli- NEC N=C cation No. 803,411 while the symmetrical esters cannot.

From the foregoing it will be apparent that one primary sfilHz SCHZ and important object of the invention resides in the pro- 3 R (II) VlSlOIl of new and novel unsymmetrical mono and diesters of cyanoimidodithiocarbonic acid.

The novel reactions described above are preferably A rela ed and also important object of the invention is carried out at reduced temperatures initially, followedby the provision of unsymmetrical cyanoimidodithiocarbona i d at an l d m t r (f 25 (1 t th ates having valuable pesticidal and growth regulating propboiling temperature of the reaction mixture). The reerties. actants are compatible with most solvent systems (e.g., Yet another related and important object of the invenwater, alcohols, acetone, hydrocarbons, and chlorinated $1011 resides in the Prevision 0f rim/e1 P11366556s for p hydmcarbons) ducing the unsymmetrical cyanoimidodithiocarbonates of Most of the novel unsymmetrical esters of the present the Present inventioninvention are obtained in the form of crystalline solids Still another related and important object of the inwhich have melting points and can be recrystallized from vention is the provision of unique synthetic intermediates conventional solvents. However, others are oils or hywhich are unsymmetrical esters of cyanoimidodithiocargroscopic liquids which can sometimes be distilled under bOIIiC acidd c d pressure, 5 Further objects and advantages and other novel features In the heretofore reported reaction most nearly re- 0f the present invention will become apparent to those sembling those of the present invention described above, Skilled in the 3118 to which this invention pertains from m t i l s,S-di t f cyanoimidodithiocarbonic the following detailed description and discussion of exacid 4 are produced by reacting two moles of an alkyleinplary embodiments of the invention and the appended 7 c arms.

These precursor salts can be prepared by reacting carbon The edlately Succeedmg l i g ghe dlsulfide cyanamide with a base as described in Annalen 331, P p of the novel unsymmetncal cyanolmldodlthlo 112333 -us"ia"i3s fl to b a immide A b t sec, for example U l at. No 3,299,122) to DAmicc. the yrfii ne i iia f ii iis iz sin d 5131 1 1 a ri r b blg iiggligibl g The symmetrical dimethyl ester of cyanoimidodithiocaramounts of mono and dlalk lated 0d t t h bonlc acid is also mentioned in US. Pat. No. 2,430,232 to Guy. of the product the nnreacteii disaliz 5 W h t e lemamder carbonates contemplated by the present invention. These examples are for purposes of illustration only and are accordingly not intended to limit the scope of the invention.

EXAMPLE 1 Preparation of potassium methyl cyanoimidodithiocarbonate stirring. After the addition was complete the reaction mixture was stirred for 0.5 hr. at C. and then for 3.5

- hr. at ambient temperature. The solution was then evaporated and the residue dried at 50 C. under vacuum. This gave 271.0 g. of solid, which was treated with 1625 dried at C. This sample was treated with 165 ml. of acetone and the resulting slurry filtered. The filtr-ate was eziizgpogited, giving 21.5 g. (88%) of product, M.P. 206- The potassium benzyl cyanoimidodithiocarbonate prepared by this process was found to have the following elemental analysis:

Calculated for C H KN S (percent): C, 43.87; H, S, 26,03. Found (percent): C, 41.23; H, 2.70; S,

Due to the poor analysis the sample was identified as its 3-chloro-5-benzylthio-1,2,4-thiadiazoie derivati-ve by treatment with sulfanyl chloride (see patent application No. 803,411). The analysis of the thiadiazole was as follows:

Calculated for C H C1N S (percent): C, 45.53; H, 2.91; S, 26.42. Found (percent): C, 45.05; H, 3.00; S, 26.66.

The following compounds were prepared in an analogous manner, giving to 98% yields:

Percent Molecular M.P. Elecalcu- Percent Compound iorrnuia 0.) men lated found Potassium p-nitrobenzyl cyanoimidodithiocarbonate otHtKNaoz fl 164-167 N 14.42 13.35 Potassium (3,4-methyienedioxy) benzyl cyanoimidodithioearbonate. CnHsKNzOzsz 214-215. 5 N 9. 65 9. 74 Potassium pentafiuorobenzyl cyanoimidodithiocarbonate rHzFs Nzsz 210. 5-2125 N 8.33 8.42

Those derivatives which showed a poor analysis were converted to the corresponding 1,2,4-thiadiazole derivative and identified as such (see patent application No. 803,411).

mi. of acetone. The resulting slurry was filtered, giving 145 g. of potassium iodide. The filtrate was evaporated and the residue washed with two 650 ml. portions of ether, which gave 125 g. of crude product (95% yield), M.P. 215.5-218.0 C. The product was recrystallized from ethyl acetate-chloroform, giving 71.7 g. of product (47% yield), M.P. 214-216 C.

The potassium methyl cyanoimidodithiocarbonate prepared by this process was found to have the following elemental analysis:

Calculated for C H KN S (percent): C, 21.15; H, 1.78; S, 37.66. Found (percent): C, 20.96; H, 1.88; S, 37.76.

The following compounds were prepared in an analogous manner, the yields ranging from 40 to 95%.

EXAMPLE 3 Preparation of potassium allyl cyanoimidodithiocarbonate NEC-N=C SCHzCH=CHz Percent Molecular M.P. Eiecalcu- Percent Compound formula C C.) ment lated ioun Potassium ethyl cyanoimidodithiocarbonate C4H5KN2S2 149-152 N 15.20 14.84 Potassium isopropyl cyanoimidodithiocarbonate C 1N2 157-167 N 14.12 14.06 Potassium n-butyl cyanoimidodithiocarbonate CBHBKN2S2 157-167 N 13.19 12. 77 Potassium n-hexyl cyanoirnidodithioearbonate.. CBHI3KN2S2 160-170 N 11.65 11.67 Potassium n-decyl cyanoimidodithiocarbonate ChHnKNzSz 116-124 N 9. 45 9.06 Potassium s-butyi cyanoimidodithiocarbonate CsHmKNzSz 180-186 N 13.13 15. 56

Samples that were difiieult to analyze or gave a poor analysis were converted to the corresponding 1, 2, 4-

thiadiazoles and identified as such (see application No. 803,411).

EXAMPLE 2 A solution of 19.4 g. (0.1 mole) of dipotassium cyanoimidodithiocarbonate in 61.5 ml. acetone and 69 ml. water was cooled to 0 C., and 12.7 g. (0.1 mole) of benzyl chloride was added in 31.5 ml. acetone with stirring. After the addition was complete the reaction mixture was stirred for 0.5 hr. at 0 C. and then for 3.5 hr. at ambient temperature. The solution was evaporated and the product produced a residue which was treated with 250 ml. of ethyl acetate, giving a slurry which was filtered. The filtrate was then evaporated, giving 47.3 g. of potassium allyl cyanoimidodithiocarbonate (97% yield), M.P. 138.2- 140" C.

The potassium allyl cyanoimidodithiocarbonate prepared by this process was found to have the following elemental analysis:

Calculated for C H KN S (percent): C, 30.59; H, 2.57; N, 14.27; K, 19.91. Found (percent): C, 29.70; H, 2.45; N, 14.28; K, 20.30.

The following compounds were prepared in an analogous manner in yields ranging from 75 to Percent Molecular MI. Elecalcu- Yereent Compound formula C.) ment lated found Potassium Z-ehloroallyl cyanoimidodithioearbonete CH4C1KN2S2 169-171 N 12.14 11.43 Potassium 3,4,4-trifluoro-3-butene eyanoimidodithiocarbonate CuHiFQKN 182 136. 5-139. 5 N 10.60 10. 73

EXAMPLE 4 acetate chloroform, giving 20 g. of yellow solid (82.5 Pre aration of otassium methox meth lc anoimidodiyield) .9387

P p thiocarbonaze y y The potassium ethoxycarbonylmethyl cyanoimidodithiocarbonate prepared by this process was found to have the SK following elemental analysis: Calculated for C H KN O S (percent): C, 29.74; H, 2.91; N, 11.56. Found (percent): C, 29.50; H, 2.81; N, 801120011; 11.76. A solution of 8.7 g. (0.05 mole) of dipotassium cyano- The following compounds were prepared in an analimidodithiocarbonate in ml. of water was cooled to 0 ogous manner in yields ranging from 70 to 100%:

Molecular Ml; P2125231; Percent Compound formula 0.) Element lated found Potassium a-aeetanllido eyanoimidodithiocarbona e mHBKNaOZ i 93-97 N 14, 52 14, 73 Potassium a-aeetamide eyanoimidodithlocarbonate G4H KN3OS; 161-163 N 19. 70 19,65 Potassium eyanomethyl eyanoimidodithioearbonate- 165-167 N 21. 52 21.65 Potassium -y-p1colyl cyanoimidodithiocarbonate CsHeKNsSz 160-170 N (dee.) 16.99 16.01

C., and 4.0 g. (0.05 mole) of chloromethyl methyl ether EXAMPLE 6 was added dropwise. After the addition was complete the slurry was stirred at 0 C. for min. and at room tem Pfepal'atlon of calcium y WaIIOimidOdiIhiO- perature for 1 hour. The solvent was then evaporated at 30 carbonate 40 C. under vacuum and the resulting residue treated with 25 ml. of acetone. The resulting slurry was filtered and the filtrate evaporated as above. The residue was treated with 25 ml. of ethyl acetate. The resulting slurry 3 g was filtered and the filtrate evaporated. This gave a prodnot which, recrystallized from ethyl acetate benzene, pro- 8 CH CH duced 4.3 g. of sample (50% yield). a): 1-2

The potassium methoxymethyl cyanoimidodithiocarbonate prepared by this process was found to have the following elemental analysis:

Calculated for C H KN OS (percent): C, 23.98; H, 2.52; N, 13.98; S, 32.01. Found (percent): C, 24.20; H, 2.10; N, 14.20; S, 32.32.

The following compounds were prepared in an analo- A solution of 8.6 g. (0.055 mole) of calcium cyano imidodithiocarbonate in 50 ml. water was cooled to 0 C., and 7.58 g. (0.055 mole) of n-butylbromide in 30 ml. acetone was added with stirring. After the addition was complete the solution was stirred at room temperature gous manner in yields ranging from 30 to 80%. overnight. The solution was then evaporated and the res- Percent; Molecular MP. Eleealeu- Percent Compound formula C.) ment lated found Potassium E-propanol eyanoimidodithiocarbonate C H KN2OS-i 124-137 N 13.07 13.17 Potassium ethoxyethyl eyanoimidodithiocarbonate. CQHnKNzOSs N Due to the extremely hygroscopic nature of this sample it was identified as its 1,2,4-thtadiazole derivative.

A solution of 19.4 g. of dipotassium cyanoimidodithiocarbonate (0.1 mole) in 75 ml. water and 75 mi. acetone was cooled to 0 C., and a solution of 11.8 g. of ethyl chloroacetate (0.1 mole) in ml. acetone was added with stirring. After the addition was complete the reaction mixture was stirred for 30 minutes at 0 C. and for 13.5 hours at room temperature. The solvent was then evaporated and the residue treated with 100 ml. of acetone.

.The resulting slurry was filtered and the filtrate evaporated, giving 25.6 g. of a yellow oil. This sample was dried under high vacuum and recrystallized from ethyl idue treated with 200 ml. of ether, resulting in the formation of two layers. The lower layer was separated and dried, giving 3.5 g. of calcium bromide. The upper layer was evaporated and the resulting residue treated with ml. of benzene. The resulting slurry was filtered, giving 5 g. (50% yield) of product, M.P. 227-231 C.

The calcium n-butyl cyanoimidodithiocarbonate prepared by this process was found to have the following elemental analysis:

Calculated for C H CaN S -H O (percent): C, 35.62; H, 4.98; Ca, 9.91. Found (percent): C, 35.60; H, 4.98; Ca, 9.89.

The following compound was prepared in an analogous manner in a yield of 50%:

CompoundSodium butyl cyanoimidodithiocarbonate Molecular formula--C H NaN S M.P. C.)200202 ElementN Percent calculated-44.27 Percent found-14.23

9 EXAMPLE 7 and ml. water was added 2.4 g. of methyl iodide (0.0717 mole) with stirring. After the addition was complete the solution was stirred overnight at room temperature. The resulting slurry was evaporated under vacuum at 40 C. This produced a solid which was treated with 100 ml. of water and filtered, giving 4.6 g. of solid after drying (100% yield), M.P. 158-160 C.

The methyl a-acetanilido cyanoimidodithiocarbonate prepared by this process was found to have the following elemental analysis:

Calculated for C H N OS (percent): C, 49.79; H, 4.18; N, 15.83 S, 24.17. Found (percent): C, 50.50; H,

The following compounds were prepared in an analtemperature. The solvent was stirred overnight at room 15 ogous manner in yields ranging from 10 to 80%:

Molecular MP. Elecaleu- Percent Compound formula C.) ment lated found Methyl ethylearbamoylrnethyl cyanoimidodlthlocarbonete O1H11N3OS2 125-126 S 29. 51 29. 26 Methyl carbamoylmethyl eyanoimldodithiocarbonate. C5H7N5OS2 152-154 S 33. 88 33.65 Methyl carboxymethyl cyanelmidoditliiocarbonate 5HeN2O2S2 105109 S 33. 71 33. 29 Methyl carbethoxy cyanoimidodithiocarbonate CeHsN2O2S2 (S) 31.39 31.68 38. 51 37. 72 Methyl cthoxycarbonylmethyl cyanoimidodithiocarbonate C7H10N202S2 34-36 H 4. 62 4.99 S 29. 38 28. 74 0 38.69 39.34 Methyl N,N-dimethyl carbamoylmethyl cyanoimidodithiocarbonate C7Hi1N OSz 102. 7103. 2 181 5.10 5. 18 29. 51 28. 72 Ethoxycarbonylmethyl butyl cyanolmidodlthiocarbonate CmHmNzOzSz N 10. 76 10. 84 Ethoxycal'bonylmethyl benzyl cyanoimidodithlocarbonate CiaH14NzOzS2 N 9.4 9. 55

Melting point not recorded because material is a viscous oil.

temperature. The solvent was then evaporated and the EXAMPLE 9 resulting semisolid treated with 150 ml. of chloroform, producing a slurry. This slurry was filtered and the filtrate Preparatloll 0f e y 6- Y Y) Y evaporated, giving 5 g. of an oil. This sample was distilled, cyanoirnrdodithlocarbonate giving 3 g. of liquid (37% yield,) B.P. 105.5106.5 C. at 0.15 mm. of Hg. /SCHI The methyl n-butyl cyanoimidodithiocarbonate prepared NECN=C by this process was found to have the following elemental analysis:

Calculated for C H KN S (percent): C, 44.65; H, 6.42; o N, 14.88; S, 34.05. Found (percent): C, 42.37; H, 5.61; 40

The following compounds were prepared in an analogous manner in yields ranging from 60 to 90% To a solution of 5.7 g. (0.033 mole) of potassium methyl cyanoimidodithiocarbonate in 10 ml. of acetone was added with stirring 5.7 g. of piperonylchloride in 10 Molecular M.P. Ele- Percent Percent Compound formula C.) ment calculated und Methyl allyl cyanolmidodithiocarbonate CnHaNzS2 S 37. 23 v 38. 34 Methyl 2-chloroallyl cyanoimidodithloearbonate CaH1C1N2S2 S 31. 02 32. 30 'Irlmethylene bis(2-chloroallyl) eyanoimidodlthiocarbonatm C1a 14C12N4 4 N 13. 17 1 88 n-Butyl n-decyl cyanolmidodithlocarbonate CuHanN2sz N 8.93 9. 03 Ethyl isopropyl cyanolmidodithiocarbonate C1Hl2 2 2 N 14.9 14.93

Melting point not recorded because material is a viscous oil.

EXAMPLE 8 Preparation of methyl a-acetanilido cyanoimidodithiocarbonate To a solution of 4.8 g. (0.017 mole) of potassium agiving 7.6 g. of solid. Recrystallization from ethanol gave 4 g. of solid (45% yield), M.P., 81-825 C.

The methyl 3,4-(methylenedioxy)-benzyl cyanoimidodithiocarbonate obtained by this process was found to have the following elemental analysis:

Calculated for C H N O S (percent): C, 49.60; H, 3.78; N, 10.52; S, 24.08. Found (percent): C, 49.10; H, 3.26; N, 10.09; S, 23.63.

The following compounds were prepared in an analoacetanilido cyanoimidodithiocarbonate in 50 ml. acetone gous manner in yields ranging from 10 to Percent Molecular M.P. Elecaleu- Percent Compound formula C.) merit lated found Methyl p-nitrobenzylcyanoimidodithlocarbonate 01011 193028 106-107. 5 N 15. 72 15. 63 Methyl benzyl cyanoimidodithiocarbonate C10H10N2s9 N 12. 60 12. 47 Methyl cyanomethyl cyanoimidodithiocarbonate. ceHsNasz 5960 S} 37. 84 34. 04

Methyl methoxymethyl eyanoimidodithioearbonate... CrHsNgOSz 3%. 3i.

' Melting point not recorded because material is a viscous oil.

1 1 EXAMPLE 10 Preparation of methyl n-butyl cyanoimidodithiocarbonate SCH:

NECN=C S(CH2);CH;

A 38.5 ml. fraction of a 1.3 molar solution of aqueous calcium cyanoimidadithiocarbonate (0.05 mole) was cooled to 5 C., and 6.8 g. of butyl bromide (0.05 mole) was added. The resulting slurry was stirred for 6 hours at room temperature. To this solution was added 7.1 g. of methyl iodide. The resulting slurry was stirred for 24 hours at room temperature. The solvent was then evaporated and the residual treated with 100 m1. of chloroform, giving a slurry which was filtered and dried over anhydrous magnesium sulfate. This gave 7.0 g. (74% yield) of product, B.P. 105-105 C. at 0.15 mm. of Hg.

Analysis confirmed that the product was the expected methyl n-butyl cyanoimidodithiocarbonate.

The following examples illustrate the exceptional capability the compounds of this invention have for regulat- 1 2 EXAMPLE 12 The compounds of the present invention also possess a high degree of post-emergence herbicidal activity. This is shown by the tests discussed below.

Spray compositions were used in the tests. These were prepared in the following manner: One and four-tenths (1.4) parts of cyanoimidodithiocarbonate for a one pound per acre rate (6.8 parts for a five pound per acre rate), seven parts of polyoxyethylene sorbitan monolaurate, and parts of denatured alcohol were thoroughly mixed together with a micromortar and pestle. The mixture was then diluted with 5000 parts of water.

The spray compositions were applied with a sprayer to Poa pratensis (A), Amaranlhus retroflexus (B), Barbarea spp. (C), and Trifolium repens (D) when the first true leaves had appeared (approximately three weeks after sowing). Similar plants were left untreated as a comparative check.

Twenty-one days after application percentage of kill was calculated using untreated plants as standards. The results are tabulated below:

Rate, Percent kill pound Compound acre A B O D Methyl N-ethyl earbamoylmethyl cyanoimidodithioearbonate 5 15 100 72 Methyl carbethoxymethyl eyanoinndodithioearbonate 5 12 83 92 Methyl allyl eyanmmldodrthtocarhonate 1 100 100 92 Methyl 2-ehloroally1 eyanormidodithiocarbonate 1 9 35 8G 56 ing the growth of biological systems. Again, the examples are for purposes of illustration only and are not intended to limit the scope of the invention.

EXAMPLE 11 The compounds disclosed herein have a high degree of pre-emergence herbicidal activity. To demonstrate this, parts of cyanoimidodithiocarbonate, 3 parts of polyoxyethylene sorbitan monolaurate (Tween 20--Atlas), and 4 parts of denatured alcohol (Synasol-Union Carbide) were thoroughly mixed together with a micromortar and pestle. This mixture was added to 1109 parts of denatured alcohol, and the resulting mixture was stirred into 5000 parts of sand. The sand mixture was stirred frequently at room temperature until dry.

The resulting granular composition was applied manually at a rate of 25 pounds per acre to flats sown with seeds of Poa pratensis (A), Poa annua (B), and Trifolium repens (C). Other flats similarly sown were left untreated as a comparative check. Twenty-one days after applica tion percentage of control of germination was calculated using the plant material in the untreated flats as standards.

The results are tabulated below:

Potassium methoxymethyl cyanoimidodithioearbonate- 97 60 As can be seen these exemplary compounds show outstanding pre-emergence activity.

The tabulated data shows that the tested compounds have a high degree of post-emergence herbicidal activity and considerable selectivity. For example, even at the five pound rate, the compounds did not damage Kentucky bluegrass (Poa pratensis) to an unacceptable extent. Yet, at the same rate, they gave substantial to complete control of Amaranirhus retroflexus; Barbarea spp. and Trifolium repens.

EXAMPLE 13 The compounds of the present invention also possess a high degree of fungicidal activity. This is shown by the following test:

For a 0.1 pound per acre rate of active material, 1 part of cyanoimidodithiocarbonate, 41 parts of polyoxyethylene sorbitan monolaurate, 396 parts acetone, and 500 parts water were mixed together with a micromortar and pestle.

A 0.2 milliliter portion of this mixture was mixed with 2.8 milliliters of water and milliliters of nutritive agar. Twenty ml. of the resulting mixture was poured into a Petri dish and allowed to set.

Three-sixteenth 55 inch plugs of Rhizoctom'a solani (A), Helmimhosporium sativum (B), and Fasarium roseum (C) were placed on the agar mixture and incubated at F. Similar fungal plugs were placed on untreated agar as a comparative check.

Seven days later percentage of kill was calculated using plugs on untreated agar as standards. The results are tabulated below:

13 The foregoing data shows that the compounds of the present invention possess a high degree of fungicidal activity, in some cases even at the remarkably low rate of 0.1 pound per acre.

EXAMPLE 14 The compounds of the present invention exhibit a high degree of insecticidal activity as shown by the data tabulated below which was obtained from tests on Drosophilia spp. (fruit flies).

This data also shows that the novel unsymmetrlcal esters of the present invention possess a much higher degree of insecticidal activity than the heretofore known symmetrical dimethyl ester of cyanoimidodithiocarbonic acid.

Percent kill at 1 hr. 3 hrs. 6 hrs.

omp ound Dimethyl cyanoimidodithiocarbonate 0 20 40 Methyl ethylearbamoylmethyl cyanoimidodrthio- 00 carbonate- 0 100 1 Methyl carbamoylmethyl cyanoimidodithiocarbono 100 100 ate Methyl carbethoxy methyl cyanolmidodithiocarbon- 0 100 100 ate Methyl allyl cyanoimidodithioearbonate 0 100 100 EXAMPLE 15 Compounds of the present invention possess a high degree of biological growth regulatory activity in the vapor phase and are accordingly valuable as fumigants. For example, applied at a rate of 20 pounds per acre, potassium isopropyl cyanoimidodithiocarbonate gave a 100% kill and 100% inhibition of Barbarea spp. (winter cress). 1

In the test in which the foregoing data was obtained, ten seeds of the test plant were presoaked for six hours at room temperature and then seeded on blotting paper previously wetted with distilled water. The seeded blotting paper was then placed in a plastic box. The active compound (80 mg.) was mixed with 50 ml. of distilled water and stirred into to grams of soil in a small, open top container.

The container with the active ingredient was placed in the plastic box, which was covered. After 18 hours the container with the active ingredient was removed from the plastic box, which was then recovered and germinated for one week at alternating temperatures of 68 to 86 F. The plastic boxes were then removed from the germinator and percentage of kill and of reduction of germination (inhibition) calculated, using untreated seeds similarly germinated as standards.

For applications of the type just described the novel compounds disclosed herein can be formulated with a variety of carriers and adjuvants into solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusts, granulates, etc. Furthermore, they may be present in such formulations in combination with one another and/or other active substances including, but not limited to, other pesticides and biological system growth regulators and plant nutrients. The following, which are hereby incorporated by reference, describe suitable carriers and adjuvants for the compounds described herein, other active ingredients with which they may be formulated, and suitable methods for preparing such formulations: U.S. Pats. Nos. 3,076,699 and 3,083,089 to Renner; Handbook of Insecticide Dust Diluents and Carriers, Watkins et al., Dorland Books, Caldwell, NJ. (1955); Chemistry of the Pesticides (3d Ed), Frear, D. Van Nostrand Company, Inc., New York, N.Y.; Weed Control (2d Ed.), Robbins et al., McGraw- Hill Book Company, Inc., New York, N.Y.; Commercial Fertilizers (5th Ed.), Collings, McGraw-Hill Book Company, Inc., New York, N.Y.; and Farm Chemicals 1969 Handbook, Meister Publishing Co., Willoughby, Ohio.

Application rates for the novel compounds described herein will vary widely depending upon the compound, the use to which it is put, and the type of formulation in which it is incorporated. Typically, however, application rates will range from 0.1 to 10 pounds per acre when the compounds disclosed herein are employed as fungicides and from 1 to 25 pounds per acre when they are employed as herbicides. In any event appropriate application rates can be readily determined by those conversant with the arts to which the present invention relates.

The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

What is claimed and desired to be secured by Letters Patent is:

1. A monoester of cyanoimidodithiocarbonic acid having the formula:

wherein (a) M is selected from the group consisting of the alkali metals;

(b) R is selected from the group consisting of hydrogen and C -C alkyl; and

(c) Z is selected from the group consisting of hydrogen, C -C alkyl, C -C alkenyl, C -C alkenyl substituted with 1-3 chlorine or fluorine atoms, phenyl, mononitrophenyl, pentafluorophenyl, C -C alkoxy, hydroxy C C alkyl, C -C alkoxymethyl, C -C alkoxycanbonyl, carbamoyl, N-phenylcarbamoyl, and cyano. 2. The monoester of claim 1, where M is selected from the group consisting of potassium and sodium.

3. A monoester of cyanoimidodithiocar bonic acid having the formula:

15 wherein:

(a) M is selected from the group consisting of the alkaline earth metals; (1)) R is selected from the group consisting of hydrogen and C -C alkyl; and (c) Z is selected from the group consisting of hydrogen, C -C alkyl, C -C alkenyl, C -C alkenyl substituted with 13 chlorine or fluorine atoms, phenyl, mononitrophenyl, pentafluorophenyl, C -C alkoxy, hydroxy C 0,, alkyl, C -C alkoxymethyl, C -C alkoxycarbonyl, carbamoyl, N-phenylcarbamoyl, and cyano. 4. The monoester of claim 3, wherein M is selected from the group consisting of calcium and magnesium. 5. Potassium methyl cyanodithioimidocarbonate.

References Cited UNITED STATES PATENTS 3,299,129 1/1967 D'Amico 260 -551 2,430,332 11/1957 Guy at al. 260 551 HENRY R. IILES, Primary Examiner H. I. MONATZ, Assistant Examiner US. Cl. X.R.

260256.5 R, 294.5 G, 329 ME, 340.3, 347.2, 481, 465.5 R, 561 S, 562 T; 7190, 92, 88, 94, 98; 424-251, 263, 275, 278, 298, 304, 320, 324

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 .658, 9 Dated April 25, 1972 Inventor 5 Richard J. Timmons and Lawrence S. Wittenbrook It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 68, change "symmetrical" to --s u netrical-.

Column 5, after "Example 2", insert ---Preparation of Potassium Benzyl Cyanodithioimidocarbonate-.

Column 6, line 9, change "26,03" to -26.03-.

Column 9, line 14, after "added" insert -with stirring.--.

Column 9, line 15, delete --temperature.-.

Column 9, line 15, change "solvent" to --solution-.

Column 10, line 12, after "15.83" insert Column 11, line 16, change "IDS-105 to --l05-l06 Signed and sealed this 6th day of March 1973.

(SEAL) 1\tteSt:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents OPP-1 PO-IOSO (10-69) USCOMM-DC 60375-F'69 Q U.5. GOVERNMENT PRINT NG OFFICE I969 O]66-334 

